The expected magnitude of simultaneous parity and time violation in nuclear systems

Time (T) and simultaneous parity-time (PT) symmetry violations in the nuclear system generally cause the gamma ray multipole mixing ratios to acquire imaginary components. These complex phases may then be measured experimentally by virtue of the resulting gamma ray distributions. However, the true significance of such experiments may only be assessed once the imaginary mixing ratios have been related theoretically to the coupling constant of some fundamental, symmetry violating, interaction. We discuss, in a quantitative way, the various aspects of this relationship. To illustrate this further we examine the case of the 1189 keV transition in¹⁸²W. For this transition we predict the experimentally observable mixing ratio to have a parity (P) violating real part of ≅5×10⁻⁵ and a PT violating imaginary part of , where is the strength of the isovector PT violating pion-nucleon coupling. An upper limit to this coupling of ≲3×10⁻¹⁰ may be obtained from the electric dipole moment of the neutron.     

Face Selectivity of the Diels-Alder Additions of Sulfur-Substituted Dienes and Tetraenes Grafted onto 7-Oxabicyclo[2.2.1]heptanes

Stereoselective synthesis of 2-methylidene-3-[(Z)-(2-nitrophenylsulfenyl)methylidene]-7-oxabicyclo[2.2.1]-heptane ( 16 ), 1,4-epoxy-1,2,3,4-tetrahydro-5,8-dimethoxy-2-methylidene-3-[(Z)-(2-nitrophenylsulfenyl)methylidene]anthracene ( 18 ), and 1,4-epoxy-1,2,3,4-tetrahydro-5,8-dimethyoxy-2-methylidene-3-[(Z)-(phenylsulfenyl)-methylidene]anthracene ( 19 ) are presented. The Diels-Alder additions of these S-substituted dienes and those of 2,5-dimethylidene-3,6-bis{[(Z)-(2-nitrophenyl)sulfenyl]methylidene}-7-oxabicyclo[2.2.1]heptane ( 17 ) have been found to be face selective and ‘ortho’ regiospecific. The face selectivity depends on the nature of the dienophile. It is exo-face selective with bulky dienophiles such as ethylene-tetracarbonitrile (TCNE) and 2-nitro-1-butene and endo-face selective with methyl vinyl ketone, methyl acrylate, and 3-butyn-2-one. In the presence of a Lewis acid, the face selectivity of the Diels-Alder reaction can be reversed. The addition of the first equivalent of a dienophile to tetraene 17 is at least 100 times faster than the addition of the second equivalent of the same dienophile to the corresponding mono-adduct. The X-ray structure of the crystalline bis-adduct 43 , a 7-oxabicyclo[2.2.1]hepta-2,5-diene system annellated to two cyclohexene rings, resulting from the successive additions of methyl acrylate and methyl vinyl ketone to tetraene 17 is presented. Only one of the two endocyclic double bonds of the 7-oxabicyclo[2.2.1]hepta-2,5-diene deviates from planarity, the substituents bending towards the endo face by 5.7°.     

Stereoselective Double Functionalization of Iron-Carbonyl Complexes of 5,6,7,8-Tetramethylidenebicyclo[2.2.2]oct-2-ene. Crystal Structure and Absolute Configuration of (–)-trans-μ-[(2S,5R,7S)-C,5,6,C-η:C,7,8,C-η-(6,7,8-trimethylidene-5-((Z)-2-oxopropylidene)-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron)

The Friedel-Crafts monoacylation of trans-η-[(1RS,2RS,4SR,5SR,6RS,7SR,8SR)-C,5,6,C-η:C,7,8,C-η-(5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron) ((±)- 5 ) is highly stereoselective and yields trans-η-[(1RS,2RS,4RS,5SR,6RS,7RS,8SR)-C,6-η,oxo-σ:C,7,8,C-η-(6,7,8-trimethylidene-5-((Z)-2-oxopropylidene)-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron) ((±)- 8 ) which equilibrates with the trans-η-[(1RS,2RS,4RS,5SR,6RS,7RS,8SR)-C,5,6,C-η:C,7,8,C-η-(6,7,8-trimethylidene-5-((Z)-2-oxopropylidene)-2-bicyclo[2.2.2]octyl acetate)]-bis(tricarbonyliron) ((±)- 9 ) on heating. Optically pure (–)- 9 has been prepared from the corresponding optically pure alcohol (+)- 4 . The structure and absolute configuration of (–)- 9 was established by single-crystal X-ray diffraction.     

Unambiguous Proof for Alcoxycarbonyl-group Migration in Wagner-Meerwein Rearrangements

In HSO₃F/SO₂ClF the β-hydroxy esters Ph-CHOH-CMe₂-COOR ( 1 , R?Me, Et) are doubly protonated, then transformed into the fluorosulfates 7 and (partly) into the fluorides 8. At ?15°, both 7 and 8 undergo a rearrangement, forming derivatives of Me₂C?C(Ph)COOR ( 2 ). By labelling 1 with ¹³C, singly (¹³C(3)) and doubly (¹³C(1,3)), it could be shown that exclusively the ROOC groups undergo a 1,2-shift. Compound 2 is also formed in HSO₃F/SO₂ClF from the isomeric Me₂COH-CHPh-COOR ( 3 ) by elimination, and less easily from the α-hydroxy ester Ph-CMe₂-CHOH-COOR (5) via a phenyl 1,2-shift. Another isomer, Ph-C(OH)Me-CHMe-COOR (4) gives products different from 2 . Using more acidic systems containing SbF₅, the free carbenium ions 13 (Ph-CH⁺-CMe₂-COOR) can be stabilized; they do not form 2 , possibly because of complexation of the ester group with SbF₅. The energy profile and the mechanism of the rearrangement 1 → 2 are discussed.     

Phosphan-, Phosphit- und Phosphido-Komplexe des Vanadiums(V)

Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds ^tC₄H₉N?VCp(NH^tC₄H₉)[P(SiMe₃)₂] and ^tC₄H₉N?VCp(NⁱProp₂)(PR₂) (R?SiMe₃, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF₂)₂V₂Cl₂)(N^tC₄H₉)₂]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [^tC₄H₉N?VCl₂ · PPh₃]⁺PF₆^? has been isolated. 1 reacts with an excess of diisopropylamine forming ^tC₄H₉N?V(NⁱProp₂)Cl₂ ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds ^tC₄H₉N?VCp(NⁱProp₂)Cl ( 3 ) and ^tC₄H₉N?V(NⁱProp₂)X₂ (X?CH₂CMe₃, O^tC₄H₉, CH₃COO) has been prepared. All compounds obtained are characterized by ¹H, ⁵¹V, ³¹P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom.     

New Nonhydrolyzable Mimetics of Sialyl Lewis X and Their Binding Affinity to P‐Selectin

Wittig olefination of (2S,3R,5S,6R)‐5‐(acetyloxy)‐tetrahydro‐6‐[(methoxymethoxy)methyl]‐3‐(phenylthio)‐ 2H‐pyran‐2‐acetaldehyde ((+)‐ 10 ) with {2‐[(2S,3R,4R,5R,6S)‐tetrahydro‐3,4,5‐tris(methoxymethoxy)‐6‐methyl‐ 2H‐pyran‐2‐yl]ethyl}triphenylphosphonium iodide ((?)‐ 11 ) gave a (Z)‐alkene derivative (+)‐ 12 that was converted into (αR,2R,3S,4R,5R,6S)‐tetrahydro‐α,3‐dihydroxy‐2‐(hydroxymethyl)‐5‐(phenylthio)‐6‐{(2Z)‐4‐[(2S,3S,4R,5S,6S)‐tetrahydro‐3,4,5‐trihydroxy‐6‐methyl‐2H‐pyran‐2‐yl]but‐2‐enyl}2H‐pyran‐4‐acetic acid ( 8 ), (αR,2R,3S,4R,6S)‐tetrahydro‐α,3‐dihydroxy‐2‐(hydroxymethyl)‐6‐{4‐[(2S,3S,4R,5S,6S)‐tetrahydro‐3,4,5‐trihydroxy‐6‐methyl‐2H‐pyran‐2‐yl]butyl}‐2H‐pyran‐4‐acetic acid ( 9 ), and simpler analogues without the hydroxyacetic side chain such as (2S,3S,4R,5S,6S)‐tetrahydro‐6‐methyl‐2‐{(2Z)‐4‐[(2S,3R,5S,6R)‐tetrahydro‐5‐hydroxy‐6‐(hydroxymethyl)‐3‐(phenylthio)‐2H‐pyran‐2‐yl]but‐2‐enyl}‐2H‐pyran‐3,4,5‐triol ( 30 ), (2S,3S,4R,5S,6S)‐tetrahydro‐6‐methyl‐2‐{[(2S,5S,6R)‐tetrahydro‐5‐hydroxy‐6‐(hydroxymethyl)‐2H‐pyran‐2‐yl]butyl}‐2H‐pyran‐3,4,5‐ triol ((?)‐ 41 ) and (2S,3S,4R,5S,6S)‐tetrahydro‐6‐methyl‐2‐{(2Z/E))‐4‐[(2R,5S,6R)‐tetrahydro‐5‐hydroxy‐6‐(hydroxymethyl)‐2H‐pyran‐2‐yl]but‐2‐enyl}‐2H‐pyran‐3,4,5‐triol ( 43 ). The key intermediates (+)‐ 10 and (?)‐ 11 were derived from isolevoglucosenone and from L ‐fucose, respectively. The following IC₅₀ values were measured in a ELISA test for the affinities of sialyl Lewis x tetrasaccharide, 8, 9, 30 , (?)‐ 41 , and 43 toward P‐selectin: 0.7, 2.5–2.8, 7.3–8.0, 5.3–5.9, 5.0–5.2, and 3.4–4.1 mM , respectively.     

Metal complexes of porphycene,corrphycene, and hemiporphycene: stability and coordination chemistry

Porphyrin (P), porphycene (Pc), corrphycene (Cn), and hemiporphycene (Hpc) represent a series of well defined "4-N in" constitutional porphyrin isomers. These isomers, in the form of their octaethyl derivatives, represent a congruent set of porphyrinoids whose properties can be compared. In this study we report how variations in electronic structure and nitrogen-core size in the free-base forms of these four systems are reflected in the properties of their corresponding metal complexes. Specifically, the effects that these differences have on the axial ligation properties of the Zn(II), Mg(II), Ni(II), and Co(II) complexes of P, Pc, Cn, and Hpc in toluene using pyridine as the axial ligand are detailed. Also reported are the relative stabilities of these complexes under acidic conditions. It is shown that for the zinc, magnesium, and cobalt complexes, there are distinct differences in the ability to maintain four-, five-, or six-coordinate geometries in the presence of similar concentrations of pyridine. By contrast, no apparent differences in axial ligand binding affinity are seen for the four nickel complexes. Little difference in stability was likewise seen when these same complexes were subject to acid-mediated demetallation, with all four falling into stability class II, according to the accepted porphyrin stability ranking system. High stabilities were also seen in the case of the cobalt complexes, with the Pc and Cn complexes being of stability class III and the P and Hpc derivatives falling into stability class II. The Zn(II) and Mg(II) complexes were all far less stable than the corresponding Ni(II) and Co(II) complexes. In this case, semiquantitative analyses of the rate of acid-induced decomposition revealed the following stability sequence P>Cn>Hpc>Pc for both the Zn(II) and Mg(II) complexes. Single-crystal X-ray diffraction structures were solved for the Zn(II), Mg(II), and Ni(II) complexes of the octaethyl derivatives of Hpc, Cn, and Pc as well as a Co(II) octamethylcorrphycene and are reported as part of this study. These solid-state structures confirm four-coordinate species for the Ni(II) complexes, four- and five-coordinate species for the Mg(II) and Zn(II) complexes, and a six-coordinate species for the lone Co(II) complex.     

Preparation and Diels-Alder Reactivity of 2,3,5,6,7,8-Hexamethylidenebicyclo [2.2.2]octane (‘[2.2.2]Hericene’). Force-field calculations of exocyclic dienes as a moiety of bicyclic skeletons

The [2.2.2]hericene ( 6 ), a bicyclo[2.2.2]octane bearing three exocyclic s-cis-butadiene units has been prepared in eight steps from coumalic acid and maleic anhydride. The hexaene 6 adds successively three mol-equiv. of strong dienophiles such as ethylenetetracarbonitrile (TCE) and dimethyl acetylenedicarboxylate (DMAD) giving the corresponding monoadducts 17 and 20 (k₁), bis-adducts 18 and 21 (k₂) and tris-adducts 19 and 22 (k₃), respectively. The rate constant ratio k₁/k₂ is small as in the case of the cycloadditions of 2,3,5,6-tetramethylidene-bicyclo [2.2.2]octane ( 3 ) giving the corresponding monoadducts 23 and 27 (k₁) and bis-adducts 25 and 29 (k₂) with TCE and DMAD, respectively. Constrastingly, the rate constant ratio k₂/k₃ is relatively large as the rate constant ratio k₁/k₂ of the Diels-Alder additions for 5,6,7,8-tetramethylidenebicyclo [2.2.2]oct-2-ene ( 4 ) giving the corresponding monoadducts 24 and 28 (k₁) and bis-adducts 26 and 30 (k₂). The following second-order rate constants (toluene, 25°) and activation parameters were obtained for the TCE additions: 3 +TCE→ 23 : k₁ = 0.591±0.012 mol^?1·l·s^?1, ΔH^≠=10.6±0.4 kcal/mol, and ΔS^≠ = ?24.0±1.4 cal/mol·K (e.u.); 23 +TCE→ 25 : k₂=0.034±0.0010 mol^?1·l·s^?1, ΔH^≠ = 10.6±0.6 kcal/mol, and ΔS^≠ = ?29.7±2.0 e.u.; 4 +TCE→ 26 : k₁ = 0.172±0.035 mol^?1·l·s^?1, ΔH^≠ 11.3±0.8 kcal/mol, and ΔS^≠ = ?24.0±2.8 e.u.; 24 +TCE→ 26 : k₂ = (6.1±0.2)·10^?4 mol^?1·l·s^?1, ΔH^≠ = 13.0±0.3 kcal/mol, and ΔS^≠ = ?29.5±0.8 e.u.; 6 +TCE→ 17 : k₁ = 0.136±0.002 mol^?1·l·s^?1, ΔH^≠ = 11.3±0.2 kcal/mol, and ΔS^≠ = ?24.5±0.8 e.u.; 17 +TCE→ 18 : k₂ = 0.0156±0.0003 mol^?1·l·s^?1, ΔH^≠ = 10.9±0.5 kcal/mol, and ΔS^≠ = ?30.1 ± 1.5 e.u.; 18 +TCE→ 19 : k₃=(5±0.2) · 10^?5 mol^?1 mol^?1 ·l·s^?1, ΔH^≠ = 15±3 kcal/mol, and ΔS^≠ = ?28 ± 8 e.u. The following rate constants were evaluated for the DMAD additions (CD₂Cl₂, 30°): 6 +DMAD→ 20 : k₁ = (10±1)·10^?4 mol^?1 · l·s^?1; 20 +DMAD→ 21 : k₂ = (6.5±0.1) · 10^?4 mol^?1 ·l·^?1; 21 +DMAD→ 22 : k₃ = (1.0±0.1) · 10^?4 mol^?1 ·l·s^?1. The reactions giving the barrelene derivatives 19, 22, 26 and 30 are slower than those leading to adducts that are not barrelenes. The former are estimated less exothermic than the latter. It is proposed that the Diels-Alder reactivity of exocyclic s-cis-butadienes grafted onto bicycle [2.2.1]heptanes and bicyclo [2.2.2]octanes that are modified by remote substitution of the bicyclic skeletons can be affected by changes inthe exothermicity of the cycloadditions, in agreement with the Dimroth and Bell-Evans-Polanyi principle. Force-field calculations (MMPI 1) of 3, 4, 6 and related exocyclic s-cis-butadienes as a moiety of bicyclo [2.2.2]octane suggested single minimum energy hypersurfaces for these systems (eclipsed conformations, planar dienes). Their flexibility decreases with the degree of unsaturation of the bicyclic skeleton. The effect of an endocyclic double bond is larger than that of an exocyclic diene moiety.